Hydrochloric Acid → Ethyl 2-bromo-2-(4-methyl-1,3-thiazol-2-yl)propanoate

To a solution of ethyl 2-(4-methyl-1,3-thiazol-2-yl)propanoate (3.91 g, 19.62 mmol) in toluene (95 mL) was added hydrochloric acid (1.77 mL, 21.58 mmol). The mixture was stirred at room temperature for 10 minutes. The mixture was cooled to 0° C. and then potassium bromide (MERCK, 2.57 g, 21.58 mmol) and hydrogen peroxide (2.37 mL, 25.5 mmol) were added. Reaction mixture was stirred at 0° C. for 5 hours, at which point TLC (1:1 EtOAc-Hex) showed reaction had gone to completion. Reaction mixture was quenched with 1N Na2S2O3 (60 mL) and saturated NaHCO3 (60 mL). Organic phase was separated and the aqueous phase was extracted with ethyl acetate (2×60 mL). Combined organics were washed with brine, dried over sodium sulfate and concentrated to give the title compound (5.02 g, 18.05 mmol, 92% yield) as a red oil. 1H-NMR (300 MHz, DMSO-d6) δ ppm: 7.41 (s, 1H), 4.23 (q, 3H), 2.33 (s, 3H), 2.28 (s, 3H), 1.20 (t, 3H). [ES+MS] m/z 278 (MH+).

1. temperatureThe mixture was cooled to 0° C.
2. customReaction mixture
3. customreaction
4. customReaction mixture
5. customwas quenched with 1N Na2S2O3 (60 mL) and saturated NaHCO3 (60 mL)
6. customOrganic phase was separated
7. extractionthe aqueous phase was extracted with ethyl acetate (2×60 mL)
8. washCombined organics were washed with brine
9. dry with materialdried over sodium sulfate
10. concentrationconcentrated

ORD record

ord-48522d978d164c8a9261f86f9035c50c

Source dataset

uspto-grants-2013_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08524750B2